title: Dinitrogen cleavage and hydrogenation by a trinuclear titanium polyhydride complex.
abstract: Both the Haber-Bosch and biological ammonia syntheses are thought to rely on the cooperation of multiple metals in breaking the strong N≡N triple bond and forming an N-H bond. This has spurred investigations of the reactivity of molecular multimetallic hydrides with dinitrogen. We report here the reaction of a trinuclear titanium polyhydride complex with dinitrogen, which induces dinitrogen cleavage and partial hydrogenation at ambient temperature and pressure. By (1)H and (15)N nuclear magnetic resonance, x-ray crystallographic, and computational studies of some key reaction steps and products, we have determined that the dinitrogen (N2) reduction proceeds sequentially through scission of a N2 molecule bonded to three Ti atoms in a μ-η(1):η(2):η(2)-end-on-side-on fashion to give a μ2-N/μ3-N dinitrido species, followed by intramolecular hydrogen migration from Ti to the μ2-N nitrido unit.
authors.affiliation: Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan.
authors.forename: Takanori
authors.initials: T
authors.lastname: Shima
authors.forename: Shaowei
authors.initials: S
authors.lastname: Hu
authors.forename: Gen
authors.initials: G
authors.lastname: Luo
authors.forename: Xiaohui
authors.initials: X
authors.lastname: Kang
authors.forename: Yi
authors.initials: Y
authors.lastname: Luo
authors.forename: Zhaomin
authors.initials: Z
authors.lastname: Hou
mesh_terms: D002384:Catalysis; D018360:Crystallography, X-Ray; D006865:Hydrogenation; D009682:Magnetic Resonance Spectroscopy; D009584:Nitrogen / Q000737:chemistry*; D014025:Titanium / Q000737:chemistry*
chemical_list: D014025:Titanium; D009584:Nitrogen